Graphite powders suited for negative electrode material of lithium ion secondary battery

ABSTRACT

A graphite powder suitable for a negative electrode material of a lithium ion secondary battery which assures a high discharging capacity not lower than 320 mAh/g is to be manufactured at a lower cost. Specifically, a graphite powder containing 0.01 to 5.0 wt % of boron and having a looped closure structure at an end of a graphite c-planar layer on the surface of a powder, with the density of the interstitial planar sections between neighboring closure structures being not less than 100/μm and not more than 1500/μm, and with d 002  being preferably not larger than 3.3650 Å, is manufactured by (1) heat-treating a carbon material pulverized at an elevated speed before or after carbonization for graphization at temperature exceeding 1500° C. or by (2) heat-treating the carbon material pulverized before or after carbonization at a temperature exceeding 1500° C. for graphization and subsequently further heat-treating the graphized material at a temperature exceeding a temperature of the oxidating heat treatment and the heat treatment in the inert gas.

This patent application is a continuation of U.S. patent applicationSer. No. 10/826,233 filed on Apr. 16, 2004, issued as U.S. Pat. No.7,214,447 on May 8, 2007, which is a continuation of U.S. patentapplication Ser. No. 09/292,834 filed on Apr. 16, 1999, issued as U.S.Pat. No. 6,764,767 on Jul. 20, 2004, the disclosure of which are hereinincorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to graphite powders having a novel structuresuitable as a carbonaceous material for a negative terminal of a lithiumion secondary battery. More particularly, it relates to graphite powdersthat are able to fabricate a negative electrode of a lithium ionsecondary-battery having a high discharge capacity and superiorcharging/discharging efficiency, a method for producing these graphitepowders, a material for a negative electrode of the lithium ionsecondary battery formed of these graphite powders, and a lithium ionsecondary battery having the negative electrode which is fabricated fromthis negative terminal material.

2. Description of Related Art

A lithium secondary battery is among non-aqueous secondary batteriesemploying lithium as an active material for a negative electrode, anoxide of a transition metal or chalcogenides, such as sulfides orselenides, as an active material for the positive electrode, and asolution of an inorganic or organic lithium salt in a non-protonicorganic solvent, as an electrolytic solution.

Since lithium is a metal having an extremely base potential, it ispossible with the battery employing this as a negative electrode to takeout a large voltage easily. Consequently, a lithium secondary battery isrecently stirring up notice as a secondary battery of high electromotiveforce and a high energy density, such that expectations are made ofapplications thereof as a distribution or portable type battery in awide range of applications, such as electronic equipments, electric carsor power storage. It is already being put to use as a small-sizedbattery.

In an early version of the lithium secondary battery, use is made of afoil-shaped metal lithium as a negative electrode material. In thiscase, a charging/discharging reaction proceeds by dissolution(ionization) and precipitation of lithium. However, since metal lithiumtends to be precipitated as a needle on the negative electrode in thereaction of Li⁺→Li, repeated charging/discharging leads to precipitationof a dendritic lithium (lithium dendrite) on the surface of the negativeelectrode. If growth of this lithium dendrite is allowed to proceed,shorting with the negative electrode tends to occur through a separator(partition), thus leading to a fatal defect of an extremely shortrepetitive charging/discharging cyclic life.

As means for solving the problem of the lithium secondary battery, it isproposed in, for example, Japanese Laying-Open Patent S-57-208079 to usea carbon material capable of storing and yielding lithium ions, such asnatural graphite, artificial graphite, petroleum coke, sintered resin,carbon fibers, pyrocarbon, carbon black etc, as a negative electrodematerial. In this case, the negative electrode material maysubstantially be formed only of the carbon material, and an electrodeoperating as a negative electrode usually can be fabricated by allowingpowders of the carbon material to be deposited on a metal currentcollector along with a suitable resin binder.

Although the electrode reaction of a lithium secondary battery, thenegative terminal of which is prepared from this carbonaceous material,is not known precisely, it may be presumed that, during charging,electrons are forwarded to the carbon material of the negative electrodeand charged to the negative polarity such that lithium ions in theelectrolytic solution are accumulated by electrochemical intercalationin the carbon material of the negative electrode charged to the negativepolarity. Conversely, during the discharging, lithium ions are desorbed(de-intercalated) from the carbon material of the negative electrode andemitted into the electrolytic solution. That is, charging/dischargingoccurs due to accumulation and emission of lithium ions in or from thenegative electrode material. Therefore, this sort of the battery isgenerally termed a lithium ion secondary battery. In the lithium ionsecondary battery, in which metal lithium is not precipitated during theelectrode reaction, there is raised no problem of deterioration of thenegative electrode due to dendritic precipitation. The lithium secondarybattery now in use is mainly of this type, that is, a lithium ionsecondary battery the negative electrode of which is formed of a carbonmaterial.

The theoretical capacity of the lithium ion secondary battery, thenegative electrode of which is formed only of metal lithium, is as highas approximately 3800 mAH. Conversely, the theoretical capacity of thelithium ion secondary battery, the negative electrode of which is formedof a lithium/graphite interlayer compound (C₆Li), is 372 mAH/g, thiscapacity being retained to be a limit or threshold capacity. It is notedthat the lithium/graphite interlayer compound (C₆Li) is an inter-layercompound in which lithium ions are packed densely in a regular patternbetween layers of graphite which is the most crystalline carbonaceousmaterial.

However, since surface activated sites which inhibit intrusion oflithium ions into the carbon material of the negative electrode and adead zone against packing of lithium ions exist in actuality in thecarbon material of the negative electrode, it has been extremelydifficult to achieve the threshold capacity of 372 mAH/g even with theuse of the high crystalline graphite as the carbon material for thenegative electrode of the lithium ion secondary battery.

Meanwhile, the carbon material may be classified into hard carbon(low-crystalline amorphous carbon) and soft carbon (high-crystallinegraphite carbon). The above-mentioned threshold capacity, which holdsfor the soft carbon, fails to hold for the hard carbon, there being amaterial manifesting a higher capacity per weight. However, the capacityper volume is lowered because of the lower density of the hard carbon.

If the graphite, as the high-crystalline carbon material, is used as thenegative electrode material, there is deposited an inactivated skin filmin the course of charging with the above-mentioned decomposition of theelectrolytic solution. Since the electrical quantity used at this timerepresents the loss, the charging/discharging efficiency [dischargingcapacity/charging capacity×100 (%)], as one of battery indices, islowered. This is a considerable demerit for a usage such as asmall-sized battery having a pre-set shape standard because the quantityof the negative electrode material needs to be estimated to a largervalue at the time of battery designing.

For approaching the discharging capacity of the lithium ion secondarybattery to the above-mentioned threshold capacity as much as possible,various proposals have so far been made as to the manufacturing methodfor the carbonaceous material for the negative electrode.

For example, it is proposed in Japanese Laying-Open Patent H-4-115458,Japanese Laying-Open Patent H-5-234584 and Japanese Laying-Open PatentH-5-307958 to use carbides of mesophase globules generated in the pitchcarbonization process. The mesophase globules are spherically-shapedparticles exhibiting optical isomerism (properties of liquid crystal)and which are generated on heat treatment of pitches for several hoursat approximately 400 to 550° C. On continued heat treatment, theglobules grow in size and coalesce to become a bulk mesophase whichexhibits optical isomerism in their entirety. This bulk mesophase canalso be used as the carbon material. However, the discharging capacityof the lithium ion secondary battery employing this negative electrodematerial is as yet rather low.

In the Japanese Laying-Open Patent H-7-282812, attempts are made toraise the regularity of the layered disposition of the graphite layersin association with graphized carbon fibers to raise the capacity of thelithium ion secondary battery. In this publication, it is stated that,on pulverizing the carbon fibers, undesirable structural defectsdifferent from the regular layer disposition of the graphite layers ofthe original carbon fibers are introduced, such that, for raising thecapacity of the lithium ion secondary battery, it is meritorious toraise the regularity of the layered disposition of the graphite layers.However, if the regularity of the layered disposition of the graphitelayers is raised in this manner, the discharging capacity of the lithiumion secondary battery is 3.16 mAH/g at the maximum, such that it is notpossible to obtain a negative electrode material of the graphite-basedcarbonaceous material having the capacity as high as 320 mAH/g orhigher.

In Japanese Laying-Open Patent H-6-187972, there is disclosed a carbonmaterial obtained on firing, at an elevated temperature, a resinobtained in turn by reacting aromatic components with a cross-likingagent in the presence of an acid catalyst. This carbon material has astructure in which a crystal area of crystallized aromatic componentsand an amorphous area of amorphized cross-linking agents co-exist and,due to the differential thermal expansion/contraction coefficientsbetween the two, numerous internal structural defects are manifested. Itis stated that not only lithium ions are introduced into an inter-layerarea to form C₆Li, but also metal lithium is occluded int thesestructural defects, as a result of which it is possible to constitutehigh-capacity lithium ion secondary battery. However, since a specialresin is used as a starting material, the cost of the material is high,thus producing economic demerits. Moreover, since the carbonaceousmaterial is the hard carbon, the capacity per unit volume is lowered. Inaddition, with this material, the charging/discharging efficiency cannotbe improved.

In the Japanese Laying-Open Patent H-3-245548, there is disclosed acarbonaceous material obtained on carbonizing an organic material. Thismaterial uses a costly organic resin material, in particular thephenolic resin, as the carbonaceous material, thus raising the cost forthe material.

This carbonaceous material is stated as exhibiting a high dischargingcapacity per unit weight exceeding the threshold capacity of 372 mAH/gfor graphite. However, since this material also is hard carbon, the truedensity is lower, specifically of the order of 1.55 g/cc. On the otherhand, the true density of graphite is as high as approximately 2.2 g/cc.Therefore, the discharging capacity per unit volume of theabove-mentioned carbonaceous material is as low as 380 mAh/g×1.55g/cc=589 mAh/cc, in comparison with the discharging capacity per unitvolume of the graphite-based material, even though the latter has alower discharging capacity of, for example, 320 mAH/g. As a consequence,the hard carbon material suffers from the problem that the batterycannot be reduced in size, such that the graphite-based material is morefavorable for reducing the battery size because of its high truedensity.

The present invention envisages to provide a graphite-based material ofhigh true density which is suited for a negative electrode material of asmall-sized high-capacity lithium ion secondary battery, even though acarbon material similar to a conventional carbon material is used inplace of special resins for carbonization, and a manufacturing methodthereof

The present inventors have proposed a high-performance negativeelectrode material in which the carbon network layer (graphite c-planarlayer) has a looped closed structure on the powder surface and in whichthe density of the interstitial planar sections between the loopedclosed structures along the graphite c-direction may be controlled torealize a charging/discharging capacity exceeding 320 mAH/g. However, aswill now be explained, this negative electrode material is in need of ahigh-temperature heat treatment at a temperature exceeding 2500° C. forgraphization, as before, while a still higher temperature exceeding3000° C. is required for realizing a higher capacity, such that furtherimprovement is required for application to industrial mass production.

FIG. 1 shows the relation between the discharging capacity and d002(FIG. 1 a) and that between d002 and the graphization temperature (FIG.1 b) in case the bulk mesophase obtained from the petroleum pitch ispulverized, carbonized and subsequently graphized by changing thetemperature. It is noted that d002 is the distance between c-axis planarlattices (interlayer distances).

It is seen that d002 is decreased with rise in the graphizationtemperature and that, with decrease in d002, the discharging capacity isincreased. This relation between the discharging capacity and d002 isreported in, for example, Iizima et al, Synth. Met., 73 (1995), 9, fromwhich it is seen that approaching d002 to close to that of naturalgraphite to raise the capacity is a commonplace technique in thegraphite-based negative electrode material (d002 of ideal naturalgraphite=3.354 Å).

However, in order to obtain a graphite material with d002=3.360 Å, thegraphizing heat treatment at an elevated temperature of the order of3000° C. is required, as may be seen from FIG. 1 b. Thus, thegraphite-based negative electrode material with a smaller value of d002,that is with a higher performance, cannot be obtained if only themeasures of elevating the temperature of the graphizing heat treatmentis resorted to.

Meanwhile, from the disturbed carbon network (condensed poly-cyclicstructure of six members of carbon), the microscopic process ofgraphization may be envisioned as being a process of ordering of thearrangement of carbon atoms to a layered graphite phase.

FIG. 2 shows an example of a disturbed network of carbon clustersobtained by a molecular dynamic method employing the Tersoff potential[J. Tersoff, Phys. Rev. Lett., 19, 2879 (1988)]. The system of FIG. 2 isa network with a potential approximately 1.3 eV higher per atom than thestructural energy of graphite. In FIG. 2, an arrow indicates a sp³ (fourligancy) carbon atoms different from sp² (three ligancy) carbon in thegraphite. In the disturbed carbon network, the presence of carbon atomswith different numbers of ligands may be easily estimated from thefollowing considerations.

FIG. 3 shows the relation between the pressure and the Gibbs free energy(enthalpy) at 0 K of diamond and graphite as calculated using theTersoff potential. It is noted that diamond and graphite representtypical examples of the sp³ (four ligancy) network and sp² (threeligancy) network, respectively. As may be seen from FIG. 3, the fourligancy carbon network and the three ligancy carbon network are stableat high pressure and at low pressure, respectively, with the two beingapproximately equal to each other in energy and stabilized at a zeropressure.

A wide variety of carbon materials are produced industrially, and a widevariety of structures of the carbon materials have been found. Thereason is that, with the structure of the carbon material, a widevariety of combinations of the two networks of substantially equallystable sp³ (four ligancy) and sp² (three ligancy) are possible. It maybe estimated from FIG. 3 that four ligancy network and the three ligancynetwork are generated in the portion of a run-of-the-mill carbonmaterial subjected to compressive distortion and to that subjected tothe tensile distortion, respectively.

The process of graphization is the process of solid-phase growth fromthe disturbed carbon network, shown in FIG. 2, to the laminar planarcarbon structure (three ligancy network). This process is felt to beaccompanied by extinguishment of the four ligancy carbon and ordering toa three ligancy network. For example, for changing from the disturbedcarbon network as shown in FIG. 2 to the planar three ligancy network,two elementary processes, namely (1) cutting of the bond of the fourligancy carbon and (2) correcting the bond angle and the bond length tosp² (three ligancy) system. This may be presumed to be accompanied by asignificant activation energy.

The process of graphization is now explained a little moretheoretically. An experimental value of d002 in natural graphite is3.3545 Å, with d002 of synthetic graphite gradually approaching that ofnatural graphite by raising the graphization temperature (see FIG. 1 b).Since graphite represents the most stable state, as does diamond,insofar as the element carbon is concerned, it may be presumed that, inthe carbon material, there exists a structural energy function for astatus parameter (<d002) as shown in FIG. 4 in the carbon material. Ifsuch relation between d002 and the structural energy is presupposed, thebehavior of d002 and the graphization temperature as shown in FIG. 1 bcan be explained qualitatively as follows: That is, the higher thetemperature, the higher becomes the possibility of the energy barrier ΔE(see FIG. 4) being surpassed thus enabling transition to crystallinityclose to natural graphite.

On the other hand, the existence of hard carbon, representing thenegative electrode material for the lithium ion secondary batteryhand-in-hand with the graphite-based carbon material, may be presumed asfollows: That is, in certain carbon network, the energy barrier ΔEcannot be surpassed at a temperature corresponding to the graphizationtemperature, thus resulting in a minimum energy value remote from thatof the natural graphite. This energy barrier ΔE is the activation energyaccompanying the growth of the of the planar three ligancy network forthe graphite from the above-mentioned disturbed network, specificallythe energy barrier required for bond re-arrangement and re-coordination.Specifically, this model indicates that re-coordination of the carbonnetwork represents the speed-regulating stage of graphization (graphitesolid phase growth).

In the elementary process of graphization, it is necessary to cut thelinkage of the four ligancy carbon. This may be presumed to beaccompanied by a, extremely large activation energy. Thus, the presentinventors directed attention to the III group elements that can formthree σ bonds. The reason is that, if the amount of the four ligancyelement carbon of the disturbed carbon network can be reduced bysubstitution by three ligancy elements, the activation energy isdiminished, so that, from the above considerations, there is apossibility of the graphization temperature being changed significantlyby small changes in the activation energy. There is, however, a problemraised as to whether or not, in the graphite network followinggraphization, the III group element can substitute the carbon elementwithout disturbing the planar structure.

If, in the lithium ion secondary battery, the graphite-based carbonmaterial is used as the negative electrode material in the lithium ionsecondary battery, the charging/discharging reaction takes place byintercalation of lithium ions to the negative electrode material. Ifthree ligancy elements are substituted such as to disturb the planarstructure, the risk is high that lithium ion intercalation isobstructed. Thus, the present inventors have searched, by the molecularorbit method, into stability of the three ligancy elements in thegraphite network, and have ascertained by the computational chemicaltechnique that boron can be substituted for carbon without disturbingthe graphite planar section, as shown in FIG. 5.

Thus, the present inventors have surmised that, if boron that can besubstituted for carbon without disturbing the graphite planar section isadded and graphization heat treatment is carried out, this element wouldact as a sort of a catalyst to render it possible to produce graphitewith small d002 at a lower energy (that is at a lower heat-treatmenttemperature) than conventionally. This point was confirmed by anexperiment.

FIG. 6 shows an example of the relation between the inter-layer distanced002 and the graphization temperature of graphite samples obtained onheat-treatment at various graphization temperatures of an as-carbonizedcarbonaceous material admixed with boron and the same material notadmixed with boron. With the material admixed with boron, a small valueof d002 can be realized with a graphization heat treatment at a lowertemperature, with the rate of change of d002 with respect to thegraphization temperature being lower than that with the material notadmixed with boron. That is, it has been found that, with the materialadmixed with boron, it is possible to produce a negative electrodematerial with a lower value of d002 and hence of a larger capacity thanthat produced with the conventional high temperature heat-treatedmaterial.

The present inventors have confirmed that if, in the previously proposedgraphite-based negative electrode material having a looped closurestructure of the carbon network layer on the surface, the carbonmaterial is subjected to graphizing heat treatment after addition of B,a negative electrode material with a higher performance can be producedinexpensively at a lower graphization temperature, and a negativeelectrode material of a higher performance can be produced at acomparable graphization temperature. This finding has led to completionof the present invention.

In the Japanese Laying-Open Patent H-3-245458, there has been discloseda high capacity carbonaceous material containing 0.1 to 2.0 wt % ofboron. However, this publication fails to disclose the effect ofaddition of boron on d002 or on heat treatment temperature. The presentinvention is reached only by simultaneously employing two elements, thatis control of the interstitial planar section density in the graphitehaving the looped closure structure as found previously by the presentinventors, and addition of boron. A principal object of addition ofboron in the present invention is to lower the temperature in thegraphizing heat treatment, with the object of boron addition beingslightly different from the object in the above-mentioned Publication.It is noted that the graphite material with a smaller d002 value can beobtained by heat treatment at a temperature lower than that usedconventionally.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 a shows an example of the relation between d002 and thedischarging capacity of a graphite material and FIG. 1 b shows anexample of the relation between the graphization temperature and d002 ina graphite material.

FIG. 2 shows an example of a disturbed carbon network by computersimulation, with an arrow indicating four ligancy carbon.

FIG. 3 shows the relation between the free energy and the pressure at anabsolute 0° of the graphite and the diamond by theoretical calculations.

FIG. 4 is a schematic view showing the relation between d002 in thegraphite-based carbon material and the structural energy.

FIG. 5 shows a stable structure in the carbon network of substitutingboron obtained by the molecular orbital method.

FIG. 6 is a graph showing the relation between the graphizationtemperature and d002 of a material admixed with boron and a material notadmixed with boron.

FIG. 7 is a typical example of photograph taken with a high resolutionelectronic microscope showing a looped closed structure of a graphitepowder obtained by a first method, with an arrow indicating aninterstitial plane.

FIGS. 8 a to 8 c are schematic views showing the results of generationof looped closed structure at the terminal end of a carbon network layerof the graphite by computer simulation, wherein FIG. 8 a shows aninterstitial planar section of a looped closed structure, FIG. 8 b is aperspective view of a looped closed structure devoid of a defect andFIG. 8 c is an end view of a looped closed structure.

FIG. 9 is a schematic view showing a surface structure in case thelooped closed structures of the graphite are of the maximum density ofthe interstitial planar sections.

FIG. 10 shows a typical photograph, taken with a high resolutionelectronic microscope, for showing the cross-section in the vicinity ofthe graphite powders having an opened surface structure, and which areobtained on oxidating heat treatment following graphizing heattreatment.

FIG. 11 is a schematic view showing layered looped closed structures atthe terminal ends of the c-planar layers (carbon network layers)appearing on the surface of the graphite powder according to the presentinvention.

FIG. 12 is a cross-sectional view showing a lithium ion secondarybattery manufactured in accordance with an Example of the presentinvention.

SUMMARY OF THE INVENTION

The present invention has been completed on the basis of the aboveinformation and resides in (1) to (4) below:

-   (1) graphite powder containing 0.01 to 5.0 wt % of boron and having    a looped closure structure at an end of a graphite c-plane layer on    the surface of a powder, with the density of the interstitial planar    sections between neighboring closure structures being not less than    100/μm and not more than 1500/μm.-   (2) A method for producing a graphite powder as defined above    including a boron addition step, wherein a carbon material    pulverized at an elevated speed before and/or after carbonization is    heat-treated at a temperature exceeding 15000 C for graphization.-   (3) A method for producing a graphite powder as defined above    including a boron addition step wherein a carbon material pulverized    before and/or after carbonization is heat-treated at a temperature    exceeding 1500° C. for graphization, the heat-treated carbon    material is surface-processed under a condition of scraping the    surface of the produced graphite powder, and wherein the    surface-processed carbon material is heat-treated in an inert gas at    a temperature exceeding 800° C.-   (4) A negative electrode material for a lithium ion secondary    battery mainly composed of the above-defined graphite powders and a    lithium ion secondary battery including a negative electrode    manufactured from this negative electrode material.

According to the present invention, graphite powders having the loopedclosed structures with a high density of the interstitial planarsections constituting LI ion intrusion sites can be manufactured from arun-of-the-mill carbonaceous material without the necessity of usingspecial expensive resin material. Moreover, since graphization proceedseven at a lower heat treatment temperature, due to a catalytic action ofboron added before the graphization heat treatment, it is possible tomanufacture graphite powders of high crystallinity with d002 not higherthan 3.3650 Å which is close to the ideal value of d002 of 3.354 Å at areduced cost.

By employing the graphite powders of high crystallinity and high densityof the interstitial planar sections of the looped closed structures,according to the present invention, as a negative electrode material ofa lithium ion secondary battery, it is possible to realize a highdischarging capacity occasionally exceeding 350 mAh/g. The batteryemploying these graphite powders serves as a lithium ion secondarybattery of a high capacity. Therefore, it is possible with the presentinvention to lower the manufacturing cost and improve the performance ofa lithium ion secondary battery.

In the present invention, the “loop-like closure” or the “looped closedstructure” in the present invention means a structure in which terminalends of the carbon network layer (graphite c-planar layer) are coupledto each other to form a loop and hence a closed structure. This loop maybe a single-layer loop as shown in FIGS. 8 b or 9, or a multi-layeredloop as shown in FIGS. 7 and 11.

The “interstitial plane” means a planar section between outwardly openedgraphite layers between two neighboring looped closed structures, asshown in FIGS. 8 a and 11. If the two looped closed structures are bothof the layered looped type, only the interstitial planar section betweenthe outermost layers of these two neighboring layered loops is openedtowards outside, so that this interstitial planar section represents theinterstitial planar section in the meaning of the present invention,whilst the a gap or an interstice between two neighboring carbon networklayers in the sole layered loop is closed with a loop and hence is notthe interstitial planar section in the meaning of the present invention.

The “density of the interstitial planar sections” is defined as thenumber of interstitial planar sections per μm in a directionperpendicular to the graphite c-plane (the planar section of the carbonnetwork layer), that is the c-axis direction as shown in FIG. 11. If theclosed structure is a of a layered loop type, this density of theinterstitial planar sections is substantially the same as the density ofthe looped closed structures in case a looped layered element is countedas one, that is the number of the looped closed structures per μm in thec-axis direction.

In general, graphite powders are constituted by a large number ofregions having different c-axis directions, equivalent to crystal grainsof the polycrystalline powders, each region, more particularly, a regionforming a lump along the c-axis direction, being termed a crystallite.With the graphite powders of the present invention, it is unnecessaryfor the entirety of the ends of the c-planar layers on the powdersurfaces of the totality of the crystallites constituting the powers topresent the above-mentioned looped closed structures. However, it isnaturally preferred that substantially the totality of the crystallitespossess these looped closed structures. The reason is that the loopedclosed structures are completely continuous and chemically stable torender intrusion of the electrolytic solution to improve thecharging/discharging characteristics.

Moreover, with the present invention, the density of the interstitialplanar sections of the looped closed structures is high, that is, thenumber of times of layering of a layered looped closed structure issmall so that the radius of curvature of the loops of the looped closedstructures is rather small. Li ions are intruded via interstitial planarsections or void type defects (see FIG. 8) into the graphite and storedtherein. The loops are the sites where defects of the carbon networklayer tend to be produced, this tendency being especially high in thelooped closed structures having a small radius of curvature. With thegraphite powders of the present invention, since there exist numerousinterstitial planar sections and void type defects, representingintrusion sites of the Li ions, the quantity of intrusion and hencestorage of the Li ions in the graphite is increased. This possiblyaccounts for the increase in the discharging capacity.

EXAMPLE OF THE INVENTION

The graphite powders of the present invention, enabling the graphizingheat treatment temperature to be lowered, contain 0.01 to 5.0 wt % ofboron. The boron content is preferably 0.02 to 3.0 wt % and morepreferably 0.02 to 1.5 wt %.

If the boron content is less than 0.01 wt %, the boron content canexhibit no substantial function as a catalyst for lowering thetemperature of graphizing heat treatment. If isolated and scattered likeatoms in the pre-graphization carbon material, the boron contentexhibits the maximum catalytic action. If the boron content is in anamount exceeding 5.0 wt %, since boron in a state of solid solution ingraphite has a concentration not higher than 3.0 wt % (see G. E. Lowell,J. Am. Ceramic. 50. (I966) 142), any remaining boron is precipitated ascarbides, such as B₄C, thus undesirably decreasing the apparentcharging/discharging capacity.

Since the principal role of the boron content in the present inventionis to lower the temperature of the graphizing heat treatment, itsuffices if boron is isolated and distributed like atoms in thepre-graphization carbon material, with the time point of boron additionbeing irrelevant. That is, boron addition may occur after carbonizationor at the time of preparation of the carbonaceous material used for thegraphizing heat treatment. Of importance is that the carbon materialused for the graphizing heat treatment contain boron preferably in anatom-like isolated and distributed state, whereby the catalytic actionfor graphization is accelerated. Therefore, as far as application toindustry is concerned, it suffices if the addition time point isselected to match the boron addition timing to the pre-existing process.For example, if carbonization and graphization are executed insuccession, it is necessary to add boron prior to carbonization. If aboron compound is added, it is preferably added before carbonization atthe latest in view of homogenization. If the carbon material is in theform of mesophase globules or bulk mesophase, boron is preferably addedduring the pitch carbonization process, inasmuch as the boron compoundin this case is decomposed during the carbonization to facilitate theformation of a material in which boron is isolated and distributed likeatoms in the carbon.

There is no particular limitation to the type of the boron compoundsused for boron addition if these compounds are able to distribute boronin isolation like atoms. Examples of the boron compounds include boroncarbide, such as BC, B₄C, B₆C, boron oxides, such as B₂O₂, B₂O₃, B₄O₃ orB₄O₅, boron oxo acids, such as orthoboric acid, metaboric acid,tetraboric acid and hypoboric acid, and salts thereof The types of boriccompounds may be suitably selected depending on the time point ofaddition.

The graphite powders according to the present invention possessmicro-structural characteristics, in addition to boric acid addition,namely that the surface of the graphite powders has a looped closedstructure of the carbon network layer and that the density of theinterstitial planar sections between the looped closed structures alongthe graphite c-axis direction is not less than 100/μm and not largerthan 1500/μm. The looped closed structures and the interstitial planarsections of the graphite powders can be observed by a photograph, takenby a high-resolution electronic microscope, showing the cross-section inthe vicinity of the graphite powders. The density of the interstitialplanar sections can be found from this microscope photograph.

If the density of the interstitial planar sections is less than 100/μm,the site of intrusion of Li ions is small, even though the graphitepowders possess the looped closed structure, to render it difficult torealize a high discharging capacity exceeding 320 mAh/g. The upper limitof 1500/μm of the interstitial planar section density corresponds to theinterstitial planar section density of the single-layer looped closedstructure shown schematically in FIG. 9, or to the maximum interstitialplanar section density theoretically predicted from the graphite crystalstructure.

In a preferred embodiment of the graphite powders of the presentinvention,

-   (1) the c-axis (002) planar section lattice distance (d002) as found    by the high-precision lattice constant measurement method by X-ray    diffraction is not more than 3.3650 Å;-   (2) the specific surface area is not larger than 1.0 m²/g;-   (3) the graphite crystallite has a diameter of 100 to 2000 Å and/or-   (4) the volume cumulative mean particle size, as found by the laser    diffraction diffusion method, is 5 to 35 μm.

The reason for above numerical limitation is as follows: If, when theabove-mentioned closed structure is used, there exist carbon atomsexhibiting relatively high reactivity by not having the closedstructure, it is likely that the reaction with an electrolytic liquidoccurs to lower the charging/discharging efficiency. For furtherimproving the charging/discharging efficiency, it is desirable to reducethe specific surface area of the graphite powders to further decreasethe reactivity with the electrolytic solution. Therefore, the specificsurface area of the graphite powders according to the present inventionis preferably not higher than 1.0 m²/g. The specific surface area can befound by the BET measurement method by N² substitution.

If the specific surface area of the graphite powders is larger than 1.0m²/g, there are occasions wherein reactivity of graphite powders withrespect to the electrolytic solution is increased to lower thecharging/discharging efficiency or the cyclic durability. Although thereis no particular limitation to the lower limit of the specific surfacearea, it is usually not lower than 0.5 m²/g. More preferably, thespecific surface area is 0.2 to 0.8 m²/g. The specific surface area isvaried mainly depending on pulverization conditions, in particular onthe pulverization time duration.

The graphite c-axis direction is the direction perpendicular to thec-planar direction. The c-axis (002) plane lattice distance (d002) isthe distance between neighboring c-planar layers, namely the inter-layerdistance. This inter-layer distance d002 is an index of crystallinity,such that, if this value becomes smaller to approach to a value of anideal graphite (=3.354 Å), the crystallinity of the graphite powdersbecomes higher. The crystallinity of the graphite powders depends on thegraphizing heat treatment, such that the higher the heat treatmenttemperature, or the longer the time, the higher is the crystallinity ofthe produced graphite powders.

In general, the lattice distance of the crystal can be determined fromthe diffraction peak of the X-ray diffraction diagram. Heretofore, thislattice distance is determined using “Method for Measuring the Size ofCrystallites and Lattice Constant of Artificial Graphite”, as prescribedby the 117th Committee of Japan Society of Promotion of Science.However, the lattice distance measured by this method is corrupted witha significantly large error such that there is a risk that the physicalproperties of a material cannot be measured accurately. Thus, thepresent invention uses a precise value of d002 as found by the precisemeasurement method for the lattice constant exploiting the least squaremethod including the diffractometer error. If the value of d002, thusfound, is larger than 3.3650 Å, the graphite powders are as yet not ofsufficient crystallinity, such that a high discharging capacityoccasionally cannot be realized. The value of d002 is preferably notlarger than 3.3600 Å.

The diameter of the graphite crystallite is the length along the c-axisdirection of the graphite crystallite (area in the powder having thesame c-axis direction) as mentioned previously. If the crystallitediameter is lower than 100 Å, there are occasions wherein thecrystallite becomes so small that the crystals are disturbedsignificantly such that lithium ions intruded from the interstitialplanar section cannot be stored efficiently. On the other hand, thecrystallite diameter exceeding 2000 Å can be realized only on prolongedgraphizing heat treatment which is not economically meritorious. Thecrystallite diameter preferably is in a range from 500 to 1500 Å.

In the present invention, the mean particle size of the graphite powdersis expressed by a volume cumulative 50% value as found by the laserdifraction scattering method. If this mean particle size is less than 5μm, the powder size occasionally is too small so that the specificsurface area is increased to lower the charging/discharging efficiencyas mentioned previously. If the mean particle size is larger than 35 μm,the packing density is lowered, and diffusion of lithium ions stored inthe inside of the powders takes prolonged time, thus occasionallylowering discharge characteristics for large current discharge or lowtemperature discharge. The preferred mean particle size is 10 to 30 μm.

Preferably, particles larger in size than 75 μm, affecting dischargingcharacteristics for large current discharge or low temperaturedischarge, or small-sized particles smaller than 1 μm, deteriorating theinitial charging/discharging properties, should be substantially absent.Moreover, there is a risk that, when graphite powders admixed withlarge-sized particles, are coated on a strip-shaped pole plate, and theresulting assembly then is wound about itself a number of times to forma spirally wound electrode member, which subsequently is sealed into abattery can, the positive and negative terminals pierce through athin-sheet-like separator approximately 20 μm thick, due to stressconcentration in the large diameter particle portion, thus causingshorting of the positive and negative terminals. This problem tends tobe raised in particles of a non-definite shape having markedly differentlengths of the long and short axes. These particles of indefinite shapeare difficult to remove on sieving. If the mean particle size exceeds 35μm, the possibility for the presence of the particles of a non-definiteshape becomes higher.

The boron-containing graphite powders of the present invention, havingthe looped closed structures of the carbon network layer, can bemanufactured by heat-treating and graphizing powders of theboron-containing carbon material at a temperature exceeding 1500° C.With this graphization, the graphite powders satisfying the condition ofthe present invention, namely the density of the interstitial planarsections of the looped closed structures of not less than 100/μm, can beproduced, if the pulverization is executed under elevated speedconditions. This manufacturing method is termed the first manufacturingmethod. However, with this first method, the interstitial planar sectiondensity of the graphite obtained is only slightly larger than 100 μm,such as 100 to 120/μm, such that an extremely high interstitial planarsection density exceeding 200/μm, can in general not be realized.

With another manufacturing method (second method), boron-containinggraphite powders, obtained on graphization, are heat-treated under acondition capable of scraping the powder surface, such as under atemperature of 600 to 800° C., and subsequently heat-treated at atemperature of from 600 to 800° C. With this method, an extremely highinterstitial planar section density of, for example, 500 to 1500 per μm,can be achieved.

The manufacturing method of the boron-containing graphite powdersaccording to the present invention is not limited to the above-describedfirst and second methods. The boron-containing graphite powders may beproduced by any suitable method if ultimately the boron-containinggraphite powders having the boron content of 0.01 to 5.0 wt % and thelooped closed structures having the interstitial planar section densitynot less than 100/μm can be formed.

There is no particular limitation to the carbonaceous material used forcarbonization and may be similar to that used conventionally for themanufacture of graphite. Examples of the carbonaceous material includecoal tar pitch or petroleum pitch, mesophase globules generated on heattreatment thereof, bulk mesophase, which is the matrix of these globule,and organic resins or materials, such as polyacrylonitrile, rayon orresins disclosed in Japanese Laying-Open Patent H-2-282812, carbonizedon heating. Most desirable carbonaceous materials are mesophase globulesand the bulk mesophase.

The carbonaceous material is pulverized and carbonized to yield a carbonmaterial. Although pulverization may be performed before and/or aftercarbonization, if the carbonaceous material is pulverized aftercarbonization, the carbon material obtained on carbonization needs to betransiently cooled, such that it is necessary to effect heating fromnear the ambient temperature at the time of subsequent high temperatureheat treatment for graphization, thus increasing thermal loss.Therefore, pulverization is preferably carried out before carbonizationin view of thermal loss. Moreover, in this case, heat treatment forcarbonization and graphization can desirably be carried out insuccession.

Since the above-mentioned closure structure is formed during thegraphizing heat treatment due to irregularities in the atomic level ofthe powder surface produced on pulverization (layer defects), it isindispensable to carry out the pulverization prior to graphization inthe first method in order to obtain graphite powders having thehigh-density closed structures. This pulverization conditionsignificantly influences the interstitial planar section density of theclosed structures of the graphite powders generated on graphizing heattreatment.

If the graphizing heat treatment precedes the pulverization, not only isthe layer defect produced in the graphite c-plane layer of graphitegenerated on heat treatment, but also the introduced closure structurelikely to be destroyed due to pulverization. Therefore, with the firstmethod, pulverization is desirably carried out so that the ultimategrain size (preferably of a range of 5 to 35 μm as described above)required for the targeted usage of the graphite powders will be realizedprior to graphization. However, moderate pulverization aimed atdisintegration or classification aimed at removal of fine particles oradjustment of mean particle size can be executed after graphizing heattreatment or, in the second method, after the last heat treatment.

In general, gas evolution from the carbonaceous material, such asmesophase, or fusion by oily contents, occur during carbonization heattreatment, thus significantly decreasing the specific surface area.During graphizing heat treatment, the specific surface area is slightlydecreased due to fusion and recombination. If the specific surface areais to be not larger than 1.0 m²/g in accordance with a preferredembodiment of the present invention, pulverization may be carried outtaking into account these changes in the specific surface area. As anexample, if the mesophase is pulverized before carbonization, it issufficient if pulverization is carried out until the mesophase specificsurface area is of the order of 5 m²/g or less. If the carbon materialis pulverized after carbonization, it suffices if pulverization iscarried out so that the specific surface area of the mesophase will beon the order of 1.1 to 1.2 m²/g. This, however, is merely illustrativesince it suffices if pulverization conditions are empirically set sothat the specific surface area of graphite powders obtained aftergraphizing heat treatment will be not larger than 1.0 m²/g.

It is noted that pulverization can be carried out using a conventionalcrusher such as q hammer mill, a fine mill, an attrition mill or a ballmill. Of these, a crusher based on impact pulverization, for example, ahammer mill or a certain type of a ball mill, is preferred. Especially,with the above-mentioned first method, the effect of the pulverizationconditions on the crystalline structure of graphite powders issignificant such that high-speed pulverization needs to be used toobtain graphite powders having the interstitial planar section densityof not less than 100/μm. In addition, in order to realize atomic levelirregularities (layer defects) uniformly on the powder surface,pulverization time exceeding a certain time duration is required. Sincespecified pulverization conditions, such as rpm or the pulverizationtime duration, differ with the type of the crushers used or with thetypes of the carbonaceous material, it is sufficient if thesepulverization conditions are empirically set so that graphite powderswith the interstitial planar section density of 100 per μm or more willbe produced after graphizing heat treatment and so that the powders ofthe desired grain size will be obtained. The pulverization conditions ofproducing graphite powders with the interstitial planar section densityexceeding 100/μm or more after graphizing heat treatment solely bygraphizing heat treatment are herein termed high-speed pulverization.

If, with pulverization by a hammer mill or an attrition mill,pulverization for longer than a pre-set time duration is carried out atan rpm of 5000 rpm or more, it is possible to obtain graphite powdershaving a closed structure with an interstitial planar section densitynot smaller than 100 μm following the graphizing heat treatment. If therpm is smaller than this, the interstitial planar section density of 100per μm occasionally cannot be realized. The rpm can be increased up toapproximately 15000 rpm. However, if the rpm is increased excessively,the specific surface area of the graphite powders obtained aftergraphizing heat treatment is increased excessively, such that aninactivated film tends to be produced at the time of initial charging ofthe lithium ion secondary battery and hence a negative electrode of ahigh efficiency occasionally cannot be produced. The pulverization timeduration is adjusted depending on the rpm. For example, in order toproduce powders of a smaller specific surface area, the rpm is reduce toa smaller value, with a shorter pulverization time duration beingpreferred. That is, although a certain length of the pulverization timeis required for increasing the interstitial planar section density,prolonged pulverization time increases the specific surface areaexcessively. In the case of a hammer mill, the preferred pulverizationcondition is 15 to 30 minutes at 5000 to 7500 rpm. This, however, ismerely illustrative, such that, if the type of the crusher or thestarting material is changed, the optimum rpm or the optimumpulverization time duration is also changed.

This high-speed pulverization may be carried out in the second method,whereby it is possible to obtain closed structure of graphite powders ofextremely high density exceeding e.g., 500 per μm. However, since theinterstitial planar section density is significantly increased by twoheat treatment operations following the graphizing heat treatment,pulverization by the second method need not be high-speed pulverization,such that the rpm of 4000 to 5000 may be used. For example, a sheeringcrusher, such as a disc crusher, may be used to effect pulverizationwith a low rpm of tens to hundreds. Because of the wide degree offreedom in the crusher or in the pulverization speed, the pulverizationconditions can be controlled more easily so that the specific surfacearea will be not larger than 1.0 m²/g.

As another pulverization method, the hammer mill and the disc crushermay be used in combination in the pulverization by the first method oronly the disc crusher may be used in combination in the pulverization bythe second method. The rpm of the hammer mill in the first method is thehigh-speed rotation, that is not less than 5000 rpm, as mentionedpreviously. Since the pulverization by the disc crusher is mainly bycleavage by sheering, it is preferably carried out after carbonizationheat treatment to aid in the pulverization. The pulverization by thedisc crusher has a merit that the crystallite diameter is easier tocontrol and in particular the crystallite diameter is larger such thatpowders of a relatively uniform particle size can be produced.

With this method, it is possible to produce graphite powders having alow-pitch closed structure, with the interstitial planar section densityexceeding 1000/μm, even with the first method of using the hammer milland the disc crusher in combination for pulverizing the carbon materialand effecting graphization heat treatment on the pulverized carbonmaterial to produce graphite powders.

The carbonization conditions for the pulverized carbonaceous materialmay be selected so that elements other than carbon contained in thestarting material on decomposition of the starting material (other thancarbon and boron if boron is contained from the outset in the startingmaterial) will be removed substantially completely. For avoidingoxidation (combustion) of carbon, this carbonization heat treatment iscarried out in an inactivated atmosphere or in vacuum. The carbonizationheat treatment temperature is usually 800 to 1500° C. and preferablyapproximately 1000° C. The heat treatment time necessary forcarbonization is 30 minutes to 3 hours for the temperature of 1000° C.,depending on the sort of the starting material or the heat treatmenttemperature.

The powdered carbon material, obtained on pulverization andcarbonization, is heated for graphization. Boron is previously added tothe powdered carbon material or is added at this stage. By the catalyticaction of boron, the temperature at which occurs the graphization(crystallization) is lowered, so that the heat treatment temperature canbe lower than if the carbon material is not admixed with boron, and thetemperature not lower than 1500° C. suffices. The upper limittemperature under the current heating technique is of the order of 3200°C. However, graphite powders with d002 markedly lower, and hence withthe performance higher than in the case of the 3200° heat-treatedmaterial not admixed with boron, can be obtained with the heat treatmenttemperature of the order of 2800° C. Thus, the usual heat treatmenttemperature in a range of 1500 to 2800° C. suffices.

Although heat treatment is carried out until completion of heattreatment, it can be completed in a shorter heat treatment time thanwith the carbon material not admixed with boron for the samegraphization temperature. The reason is that the reaction ofgraphization proceeds speedily by the graphization catalyzing actionproper to boron. The graphization heat treatment time necessary forsufficient graphization, which conventionally is 30 minutes to 10 hours,is reduced in accordance with the present invention to 15 minutes to 5hours, usually to one hour or less, due to the presence of boron,depending on the temperature or the processing quantity. The heattreatment atmosphere in this case is a non-oxidizing atmosphere,preferably a non-active gas atmosphere or vacuum.

The boron-containing graphite powders, generated by this graphizationheat treatment, usually has, on the powder surface, a closed structurein which the c-planar layer terminal portions are closed in a loop. Ifthe pre-heat-treatment pulverization is effected under a sufficientlyhigh speed condition, graphite powders having the interstitial planarsection density slightly exceeding the interstitial planar sectiondensity of 100 per μm can be produced. It is noted that, ifpulverization is effected using the hammer mill and the disc crusher incombination, the interstitial planar section density becomessignificantly higher. The resulting graphite powders are the graphitepowders produced by the first method. Thus, if the interstitial planarsection density is of the order of 100 per μm, the discharging capacitycan be significantly improved than if the density is lower than 100 perμm. It has also been found that, by adding boron, it is possible toproduce graphite powders affording a discharging capacity higher thanwith a 3200° C. heat-treated material not admixed with boron by heattreatment at a temperature of the order of 2500° C.

With the second method, the boron-containing graphite powders from theabove-described graphizing heat treatment, or graphite powders obtainedon pulverizing natural graphite, are occasionally admixed with a boronsource and mixed together. The resulting mixture is heat-treated twicefurther by oxidizing heat treatment or heat treatment for scraping offother surfaces, and by heat treatment under an inert gas atmosphere, toraise the interstitial planar section density of the looped closedstructures significantly. The heat treatment after the graphization inthis second method is now explained.

The oxidizing heat treatment, effected initially on the graphitepowders, is carried out for scraping off the surface of the powderedcarbon network layer by oxidization in order to open the looped closedstructures generated by the graphizing heat treatment transiently. Thissevers the loop on the powder surface (terminal end of the carbonnetwork layer or the c-planar layer) to provide graphite powders havinga layered structure of the carbon network layers in which the terminalends of the carbon network layer are scarcely coupled to other carbonnetwork layers and in which the terminal ends of the carbon networklayer are aligned in a flatter state, as shown in FIG. 10.

Although there is no particular limitation to the conditions foroxidizing heat treatment provided that the looped closed structures areopened on oxidation, the heat treatment temperature is preferably on theorder of 600 to 800° C. The reason is that graphite powders having thelooped closed structures are high in oxidation resistance and are lesssusceptible to oxidation at a temperature lower than 600° C., with theoxidation proceeding rapidly at higher than 800° C. to acceleratedeterioration of the graphite powders in their entirety. The oxidizingheat treatment time is usually one to ten hours depending on thetemperature or the processing volume. The heat treatment atmosphere isan oxygen-containing atmosphere which may be pure oxygen atmosphere or amixed atmosphere of oxygen and inert gases.

Since the powder surface is removed by this oxidizing heat treatment,the graphite powders loses weight by approximately 2 to 5%, with thepowder size being slightly decreased by, for example, 1 to 2 μm. Ifnecessary, this decrease in particle size is taken into account insetting the conditions for pulverization.

The processing for opening the looped closed structures is not limitedto the oxidizing heat treatment. That is, any other suitable method maybe used provided that the method used permits the surface structure ofthe graphite powders to be scraped off to open the looped closedstructures to produce a layered structure of the flat carbon networklayer. As the other method, there is, for example, a fluorinating heattreatment or a hydrogenating heat treatment. The heat treatmentconditions in this case can be suitably set by experiments so as topermit opening of the looped closed structures.

If then the graphite powders are heat-treated in an inert gasatmosphere, the terminal ends of the open structure of the carbonnetwork layer is connected to the terminal end of the other carbonnetwork layer in a loop to constitute again a looped closed structure onthe surface of the graphite powders.

When the terminal ends of the carbon network layers are connected in aloop, the terminal ends of the carbon network layer on the graphitepowder surface are flattened by oxidizing heat treatment. Therefore, twoseparated layers are interconnected only on extremely rare occasions,such that a large looped closed structure made up of a large number ofloops of carbon network layers is hardly produced. The number of layersof the loops is 5 at most and usually 1 to 3. The result is that thenumber of the looped closed structures per unit length along the c-axisdirection is increased to raise the interstitial planar section density.Specifically, interstitial planar section pitch can be reduced so thatthe interstitial planar section density, which is of an order ofmagnitude only slightly exceeding 100 per μm in the first method, can beincreased to a large interstitial planar section density exceeding 200per μm and even exceeding 500 per μm in the second method.

The inert gas atmosphere may be one or more of, for example, Ar, He orNe. The heat treatment temperature which is able to induce latticevibrations of relatively large amplitude sufficient to interconnectgraphite layers suffices. The looped closed structures obtained oninterconnection are lower in energy and higher in stability. Thus,sufficient lattice vibrations are produced on heat treatment in theinert gas atmosphere to interconnect opened terminal ends of the carbonnetwork layers. To this end, the heat treatment at atemperature-exceeding 800° C. is required. Although there is noparticular limitation to the upper limit temperature, the practicalmaximum heating temperature under the current heating technique is ofthe order of 3200° C. The heat treatment time sufficient to form thelooped closed structures may be used, and in general is 1 to 10 hours,although the processing time differs significantly with temperature andthe processing quantity. For 1000° C., for example, the heat treatmenttime is approximately five hours.

During the oxidating heat treatment and the heat treatment in an inertgas atmosphere, the specific surface area of graphite powders is variedsignificantly. That is, graphite powders on oxidating heat treatment isroughed on its surface and has its closed structure opened, thus itsspecific surface area being increased. However, if the closed structureis again formed by the next heat treatment in the inert gas atmosphere,the specific surface area is decreased to revert to the specific surfacearea of the graphite powders prior to oxidating heat treatment, as hasbeen confirmed by our experiments. Thus, ultimately, the specificsurface area of graphite powders obtained on graphizing heat treatmentis substantially maintained, so that the specific surface area can becontrolled mainly by the pulverization conditions and the heat treatmentconditions of carbonization and graphization.

With the second method, in distinction with the second method,interstitial planar section density can be increased by the second heattreatment following the graphization, so that pulverization need not behigh-speed pulverization, while it can be performed after graphization.

If necessary, graphite powders obtained by the first or second methodare classified to adjust the mean particle size. This classificationneed not be performed as the last operation. Thus, it can be performedat any stage followings pulverization and may also be performed twice ormore at different stages.

The boron-containing graphite powders, having the looped closedstructures on their surfaces, according to the present invention, arerelatively low in boron contents, and hence may be used for the sameapplication as that for the conventional graphite powders. Since theterminal ends of the carbon network layer (c-planar layer) of graphiteare closed in a loop, and the density of the interstitial planarsections, as the intrusion site for lithium ions, is as high as 100 to1500 per μm, the intercalating functions proper to graphite, such asdoping, occlusion or insertion, are improved, so that other substancessuch as lithium ions can be stored in large quantities. Moreover, sincethe graphization temperature can be lowered significantly by thegraphization catalyzing action proper to graphite, the graphite materialimproved in economic merits and storage functions can be furnishedinexpensively.

Therefore, the graphite powders according to the present invention areparticularly suited as the negative electrode material of the lithiumion secondary battery. Since the graphite powders according to thepresent invention have numerous interstitial planar sections and voidtype defects, as the main intrusion sites for Li ions, Li ions can beintruded easily, such that more Li ions than conventionally get to thegraphite storage region to increase the Li ion storage quantity. Theresult is that a lithium ion secondary battery having improveddischarging capacity can be produced. Since the carbon network layer ofgraphite has the looped closed structures, which render it difficult forthe electrolytic solution to be intruded into the graphite, thecyclic-durability in case of repeated charging/discharging is prolonged.Moreover, in the preferred embodiment, the charging/dischargingefficiency is simultaneously improved due to the small specific surfacearea.

If the graphite powders of the present invention are used for thispurpose, the negative electrode of the lithium ion secondary batteryemploying the graphite powders may be manufactured by the same method asthe conventional method. In general, the graphite powders are turnedinto an electrode by molding the graphite powders on a current collectorusing a suitable binder. That is, the negative electrode material iscomposed of graphite powders as a main constituent and a small amount ofa binder. However, the electrode may also be a sintered negativeelectrode composed essentially only of graphite powders. As a currentcollector, an optional metal foil, such as a copper foil, e.g., anelectrolytic copper foil or a rolled copper foil etc, which is able tocarry graphite powders satisfactorily and which is not susceptible toelution on decomposition when used as a negative electrode, can beemployed.

The above-mentioned molding can be executed by any suitable methodconventionally used for preparing an electrode from powdered activematerials. There is no particular limitation to the molding methodsinsofar as the performance of the graphite powders as the negativeelectrode is sufficiently manifested and the powders can be moldedsatisfactorily with high chemical and electrical stability. Among thepreferred molding methods, there are a screen printing method, a thermalpressure bonding method and a slurry coating method. The scree printingmethod includes adding a binder composed of fluorine resin powders, suchas powders of polytetrafluoroethylene, polyvinylidene fluoride etc andan organic solvent such as isopropyl alcohol to graphite powders,kneading the respective components together to a paste, and screenprinting the resulting paste on the current collector. The thermalpressure bonding method adds resin powders, such as polyethylene orpolyvinyl alcohol powders, to graphite powders, dry mixing therespective components, molding the resulting mixture by hot-pressingusing a metal mold and simultaneously thermally affixing the moldedproduct onto the current collector. Finally, the slurry coating methodslurrying the graphite powders in a solvent, such as N-methylpyrrolidone, dimethyl formamide, water or alcohol, using theabove-mentioned water-soluble caking agent, such as carboxy methylcellulose, or powders of fluorine resin, as a binder, coating thisslurry on the current collector and drying the coated current collector.

The graphite powders of the present invention can be combined with anon-aqueous electrolytic solution, obtained on dissolving lithiumcompound in a suitable organic solvent, and an active material for apositive electrode, that can be used for the lithium ion secondarybattery, to fabricate a lithium ion secondary battery.

As the active material fort the positive electrode, use may be made oflithium-containing transition metal oxides LiM¹ _(1-x)M² _(x)O₂ or LiM¹_(2y)M² _(y)O₄, where x and y are numerical figures such that 0≦x≦4 and0≦y≦1, M¹ and M² denote at least one of transition metals of Co, Ni, Mn,Cr, Ti, V, Fe, Zn, Al, In and Sn, transition metal chalcogen compounds,vanadium oxides, such as V₂O₅, V₆O₁₃, V₂O₄ and V₃O₈, lithium compoundsthereof, chevrel phase compounds represented by the general formulaM_(x)Mo₆S_(8-y), where x and y are numerical figures such that 0≦x≦4 and0≦y≦1, and M is a metal, especially a transition metal, activatedcharcoal, active carbon fibers etc.

There is no particular limitation to the organic solvents used in thenon-aqueous electrolytic solution. Examples of the organic solventinclude one or more of propylene carbonate, ethylene carbonate, dimethylcarbonate, diethyl carbonate, 1,1- and 1,2-dimethoxy ethane,1,2-diethoxy ethane, γ-butyrolactam, tetrahydrofuran, 1,3-dioxolan,4-methyl-1,3-dioxolan, anisole, diethyl ether, sulforan, methylsulforan, acetonitrile, chloronitrile, propionitrile, trimethyl borate,trtramethyl silicate, nitromethane, dimethyl formamide, N-methylpyrrolidone, ethyl acetate, trimethyl ortho-formate and nitrobenzene.

As the lithium compounds of the electrolytes, use may be made of organicor inorganic lithium compounds soluble in the organic solvents used.Examples of suitable lithium compounds include one or more of LiClO₄,LiBF₄, LiPF₆, LiAsF₆, LiB(C₆H₅), LiCl, LiBr, LiCF₃SO₃ or LiCH₃SO₃.

EXAMPLES

The present invention is hereinafter explained with reference toExamples and Comparative Examples. These Examples are merelyillustrative and are not intended to limit the present invention. Inthese Examples and Comparative Examples, the graphite powders weremeasured in the following manner.

-   B content: measured in accordance with the chemical analytic method    for high-purity graphite materials prescribed in JIS R7223.-   Particle Size Distribution: measured using a laser    diffraction/scattering type grain size measurement device.-   Specific Surface Area: found by a BET-one point measurement method    by the N₂ substitution method.-   Crystallite Size: found by analyzing the 002 diffraction peak of the    powder method X-ray diffraction diagram based on the 117th Committee    of Japan Society of Promotion of Science. The 002 diffraction peak    was measured under the condition of the acceleration voltage of 40    kV, the current intensity of 150 mA and a measurement range of 20 to    90°, using an X-ray diffractometer manufactured by Mac Science Inc.    Although the upper limit of the crystallite diameter as prescribed    by the 117th Committee of Japan Society of Promotion of Science is    1000 Å, the same method is directly applied to samples exceeding    1000 Å to calculate the crystallite diameter. d002: a value    calculated by the lattice constant precision measurement method by    the least square method, inclusive of the diffractometer error, from    the X-ray diffraction diagram (inner standard not being used). The    totality of peak positions of the surface indices (002), (100),    (101), (004), (110), (112), (006) of the X-ray diffraction diagram    were used. X-ray diffraction measurement was carried out thrice and    a weighted mean of the obtained values was found as being the value    of d002.

Example 1

The present Example 1 illustrates manufacture of boron-containinggraphite powders having the looped closed structures of the presentinvention by the first method.

Using an impact crusher (“hammer mill μ-miser” manufactured by FujiPowdal), the bulk mesophase obtained from coal tar pitch was pulverizedfor five minutes per 10 kg at an rpm of 7500. The resulting bulkmesophase powders were carbonized on heating at 1000° C. for one hourunder an argon atmosphere for carbonization in order to produce powdersof a carbon material. To these powders of the carbon material were addedpowders of B₄C (boron carbide) having the size not larger than 45 μm inan amount of 0.01 to 6.5 wt % of B referred to the total amount of theaddition product. The resulting mass was mixed together mechanically andthe resulting powder mixture was heat-treated in an argon atmosphere for30 minutes at a temperature of 2500 to 3000° C. for graphization inorder to obtain graphite powders.

In these graphite powders, looped closed structures were clearlyobserved from a photo taken with a high resolution electronicmicroscope, as exemplified in FIG. 7, in which an arrow denotes aninterstitial planar section. The density of the interstitial planarsections as found from the photo was only slightly in excess of 100 perμm at optional heat treatment temperatures. The B content and d002 ofthe graphite powders were found as described above.

The produced graphite powders were classified and used for thepreparation of the electrodes in the following manner. The mean particlesize of the graphite powders was approximately 15 μm.

90 parts by weight of the graphite powders and 10 parts by weight weremixed in a solvent N-methyl-pyrrolidone, dried and formed into a paste.The resulting paste-like negative electrode material was coated to auniform thickness on a copper foil 20 μm thick, acting as a currentcollector, using a doctor blade, and was dried at 80° C. A test piece,having an area of 1 cm², sliced from the resulting product, was used asa negative electrode.

The evaluation of the negative electrode characteristics was carried outby a constant current charging/discharging test by a three electrodecell employing metal lithium for a counter-electrode and a referenceelectrode. The electrolytic solution used was a 1 mol/lit solution ofLiClO₄ in a mixed solvent of ethylene carbonate and dimethyl carbonate.

The discharging capacity was measured by charging at a current densityof 0.3 mA/cm² until a vs-Li reference electrode (vs Li/Li+) potentialreached 0.0 V and by discharging at the same current density until thevs-Li reference electrode (vs Li/Li+) potential reached +1.50 V. Thecharging capacity/discharging capacity ratio (%) was calculated and usedas a charging/discharging efficiency. The results are shown in Table 1,in which there are also shown the inter-layer distance values d002 asmeasured by the X-ray diffraction method.

Example 2

The present Example 2 illustrates the manufacture of boron-containinggraphite powders having the looped closed structures of the presentinvention by the second method.

The bulk mesophase pitch, obtained from the coal tar pitch, waspulverized, carbonized, admixed with B₄C powders andgraphizing-heat-treated in the same way as in Example 1 to producegraphite powders. The temperature for the graphizing heat treatment of2500° C. was used.

The resulting graphite powders were subjected to oxidating heattreatment in the pure oxygen atmosphere at 700° C. for three hoursfollowed by heat treatment in the Ar atmosphere at 1000° C. for fivehours.

A high resolution electronic microscope photograph of the cross-sectionin the vicinity of the surface of the graphite powders from theoxidating heat treatment indicated that the looped closed structures asseen on the surface of the graphite powders (FIG. 7) were substantiallycompletely opened to present a flat open surface structure.

A high resolution electronic microscope photograph after heat-treatingthe graphite powders heat-treated in an Ar atmosphere after theoxidating heat treatment indicated that looped closed structures wereagain formed on the powder surface opened by the oxidation processing.The density of the interstitial planar sections, as found from thisphoto, was approximately 770/μm, which is approximately one-half thetheoretical maximum density of the interstitial planar sections of1500/μm for the case of single-layer loops. Therefore, an average numberof loop layers of each looped closed structure is approximately 2.

Using the graphite powders, the electrodes were prepared in the same wayas in Example 1, at the same time as the performance of the negativeelectrode was evaluated. The results are shown in Table 1 along with themeasured values of the B content and d002.

In the preferred Example, the density of the interstitial planarsections was 770/μm, as mentioned previously. However, if heat treatmentin the Ar atmosphere after the oxidating heat treatment is carried outmore moderately, such as at a lower temperature, coupling to remotecarbon network layers is less liable to occur thus increasing thedensity of the interstitial planar sections.

Comparative Example 1

The bulk mesophase obtained from the coal tar pitch was pulverized,carbonized and graphizing-heat-treated in the same way as in Example 1to produce graphite powders. It is noted that boron was not added andthat the graphizing heat treatment was carried out at 2500 to 3000° C.

From a photograph of a high resolution electronic microscope of theproduced high resolution electronic microscope, the density of theinterstitial planar sections was measured. It was found that the densityof the interstitial planar sections was approximately equivalent to thatof Example 1, that is slightly above 100 per μm, for any heat treatmenttemperatures used.

Using these graphite powders, the electrodes were prepared and theperformance of the negative electrode was evaluated, in the same way asin Example 1. The results are shown in Table 1, along with the measuredvalues of the B content and d002.

TABLE 1 density of graphization interstitial discharging charging/amount of analyzed value temperature planar sections capacitydischarging addition of of B quantity Ex. Nos. method (° C.) per μm d002(Å) (mAh/g) efficiency (%) B₄C (wt %) (wt %) Ex. 1 1 2500 108 3.356 34192 5.0 4.1 2800 110 3.355 342 93 5.0 4.0 3000 105 3.354 344 93 5.0 4.02500 104 3.362 328 94 0.011 0.01 2500 107 3.354 340 92 5.3 5.0 Ex. 2 22500 770 3.357 357 92 5.0 3.9 Comp. 1 2500 107 3.370 305 94 — ND Ex. 12800 109 3.367 321 93 — ND 3000 105 3.366 325 93 — ND

As may be seen from Table 1, a sample not admixed with boric acid hasthe interlayer distance d002 of the c-plane layer is 3.370 Å, andremains at 3.363 Å even if the heat treatment temperature is raised to3000° C., such that the interlayer distance d002 cannot approach to anideal value of 3.354 Å.

If, in accordance with the present invention, a small amount of boron isadded to effect graphizing heat treatment, d002 becomes smaller to 3.354to 3.363 Å depending on the amount of addition of boron, even if theheat treatment temperature is relatively low at 2500° C. Thus, d002becomes smaller than its value for the heat treatment temperature of3000° C. without addition of boron. If the heat treatment temperature isincreased, d002 tends to be smaller. However, the effect of the amountof boron addition on d002 is larger than that of heat treatmenttemperature. Thus, graphite powders with a low value of d002 may beobtained by addition of boron even if the heat treatment temperature islow.

That is, d002 cannot be lowered beyond approximately 3.360 Å, in theabsence of boron addition, even if the heat treatment temperature israised significantly. However, if boron is added, d002 can be made lowerthan 3.360 Å at a lower heat treatment temperature, while the idealvalue of 3.354 Å can also be achieved, as may be seen from Table 1.

There is a high correlation between the d002 value and the dischargingcapacity, as may also be seen from Table 1, such that, the smaller thevalue of d002, the larger becomes the discharging capacity. Therefore,addition of boron that is able to realize a small value of d002 bylow-temperature graphization is effective to increase the dischargingcapacity. Moreover, if the second method, in which the looped closedstructures are opened after graphizing heat treatment and subsequentlyagain closed, is used, the density of the interstitial planar sectionsis markedly increased, that is the pitch of the interstitial planarsections is markedly smaller. This increase in the density of theinterstitial planar sections also further increases the dischargingcapacity.

It has been shown that, by lowering the graphization temperature byboron addition and by controlling the looped closed structures,according to the present invention, a negative electrode material for alithium ion secondary battery having a discharging capacity exceeding330 mAh/g can be achieved even with the graphizing heat treatmenttemperature of 2500° C. It has also been shown that the looped closedstructures can be controlled in the same way as in the case of thematerial not admixed with boron without regard to boron addition.

Example 3

Using the bulk mesophase, obtained from the coal tar pitch, and to whichwas added 1 wt % of B₄C prior to graphizing heat treatment, graphitepowders were produced by the first method, as in Example 1. The rpm ofthe crusher used for pulverizing the bulk mesophase, as a startingmaterial, was set to 7500, with the pulverizing time duration beingchanged. The graphizing heat treatment was carried out at 2500° C. The Bcontent of the produced graphite powders, sieved to 5 to 63 μm, thedensity of the interstitial planar sections of the closure structure,d002 and the specific surface area are shown in Table 2 along with thepulverizing conditions. The results of measurement of the performance ofthe negative electrode of these graphite powders, that is thedischarging capacity and the charging/discharging efficiency, are alsoshown in Table 2. The discharging capacity and the charging/dischargingefficiency were measured as stated in Example 1.

Example 4

Using the bulk mesophase, obtained from the coal tar pitch, graphitepowders were prepared by the second method, as in Example 2. B₄C wasadded and mixed prior to graphizing heat treatment. The rpm of thecrusher used in pulverizing the bulk mesophase as the starting materialwas set to 7500, with the pulverizing time being changed. The graphizingheat treatment was carried out at 2500° C.

The B content of the produced graphite powders, sieved to 5 to 63 μm,the density of the interstitial planar sections of the closurestructure, d002 and the specific surface area are shown in Table 2 alongwith the pulverizing conditions. The results of measurement of thedischarging capacity and the charging/discharging efficiency of thesegraphite powders are also shown in Table 2.

Comparative Example 2

Using the bulk mesophase, obtained from the coal tar pitch, the graphitepowders were prepared by the first method in a similar manner to Example3, that is by performing graphizing heat treatment at 2500° C. afteraddition of 1 wt % of B₄C. However, the rpm of the crusher was loweredto 4500 rpm, with the pulverization time duration being also changed.

The B content of the produced graphite powders, sieved to 5 to 63 μm,the density of the interstitial planar sections of the closurestructure, d002 and the specific surface area are shown in Table 2 alongwith the pulverizing conditions. The results of measurement of thedischarging capacity and the charging/discharging efficiency of thegraphite powders are also shown in Table 2.

TABLE 2 density of charging/ interstitial specific dischargingdischarging rpm of pulverizing planar B content surface area capacityefficiency Ex. Nos. method crusher time (min) sections/(μm) d002 (Å) (wt%) (m²/g) (mAh/g) (%) Ex. 3 1 7500 5 103 3.357 0.76 0.56 343 96 15 1043.356 0.73 0.61 342 96 30 105 3.356 0.84 0.99 343 91 45 104 3.356 0.811.51 341 85 60 106 3.356 0.72 2.99 342 81 Ex. 4 2 7500 5 771 3.356 0.740.57 356 96 30 769 3.357 0.75 1 357 90 Comprising: 1 4500 5 81 3.3580.74 0.56 317 94 Ex. 2 45 79 3.357 0.76 0.99 315 89 100 80 3.357 0.72 3316 82

In the above Table, the crystallite diameter ranges between 232 and 264Å, with the mean particle size being approximately 15 μm.

As may be seen from Table 2, the longer the pulverizing time duration,the larger becomes the specific surface area of the produced graphitepowders. However, the density of the interstitial planar sections andhence the discharging capacity were substantially not affected by thespecific surface area. As in Table 1, a high discharging capacityexceeding 340 mAh/g was obtained when the density of the interstitialplanar sections exceeds 100/μm. In particular, with the graphite powdershaving the high density of the interstitial planar sections, obtained bythe second method, an extremely high value of the discharging capacityexceeding 355 mAh/g is achieved.

On the other hand, the specific surface area influences thecharging/discharging efficiency, such that, with the specific surfacearea exceeding 1.0 m²/g, the charging/discharging efficiency is lowered,whereas, if the specific surface area is smaller than 1.0 m²/g, a highcharging/discharging efficiency not lower than 90% is achieved.

It is also seen from comparison of Examples 3 and 4 that, if oxidatingheat treatment and heat treatment in an inert atmosphere are carried outafter the graphizing heat treatment to lower the pitch in accordancewith the second method, the specific surface area is substantially notchanged.

If the rpm of the crusher is low, that is if the pulverization is notcarried out at an elevated speed, as in Comparative Example 2, thedensity of the interstitial planar sections remains to be on the orderof 80/μm, such that the discharging capacity is at a lower value between310 and 311 mAh/g, even though B is contained in the graphite powders.

Example 5

The present Example 5 is directed to manufacture of graphite powdershaving the closure structure of the present invention by the firstmethod.

A bulk mesophase pitch, obtained from the coal tar pitch, was carbonizedat 1000° C. in an argon atmosphere to produce a carbon material whichwas pulverized so that approximately 90 vol. %. of the powders is withinthe particle size range of 1 to 80 μm. For pulverization, a hammer milland a disc crusher were used in this order. The hammer mill used was thesame as that used in Example 1, with the rpm ranging between 6000 and8000. The disc crusher with the rpm ranging between 50 and 200 rpm wasused. The pulverization time duration was set to five minutes forpulverization by the hammer mill and that by the disc crusher.

The carbon material, pulverized by the hammer mill and the disc crusher,was admixed with 1 wt % of B₄C, as in Example 1, and the mixture wasthen heat-treated for graphization at 2500° C. in order to producegraphite powders.

The measured results of the B content, density of the closure structure,specific surface area, crystallite diameter, mean particle size,discharging capacity and the charging/discharging efficiency are showncollectively in Table 3 along with the rpm of the crusher.

Example 6

The present Example is directed to manufacture of graphite powdershaving the closure structure of the present invention by the secondmethod.

A bulk mesophase pitch, obtained from the coal tar pitch, was carbonizedat 1000° C. in an argon atmosphere to produce a carbon material whichwas then pulverized so that approximately 90 vol. % of the powders willbe in a particle size range of from 1 to 80 μm. The carbon material waspulverized using only a disc crusher which was used in a rpm rangingbetween 50 and 200.

The carbon material pulverized by the disc crusher was admixed with 1 wt% of B₄C, as in Example 2. The resulting mixture was graphizing heattreated at 2500° C. subsequently processed with oxidating heat treatmentand heat treatment in an argon atmosphere.

The measured results of the B content, density of the closure structure,specific surface area, crystallite diameter, mean particle size,discharging capacity and the charging/discharging efficiency are showncollectively in Table 3 along with the rpm of the crusher.

TABLE 3 density of charging/ interstitial specific crystallite meandischarging discharging rpm planar sections B content surface areadiameter particle size capacity efficiency method hammer disc (μm) (wt%) (m²/g) (Å) (μm) (mAh/g) (%) Ex. 5 1 6000 50 106 0.78 0.98 1947 22.5348 93 6000 200 107 0.74 0.92 204 21.9 340 94 6000 150 104 0.76 0.891238 21.8 344 92 6700 150 9.4 0.75 0.93 1147 20.9 358 91 7400 150 12980.72 0.91 987 22.1 359 92 8000 150 1475 0.81 0.94 1189 19.4 361 94 Ex. 62 — 50 765 0.82 0.88 1768 19.7 349 93 — 150 943 0.79 0.91 1224 18.7 34491 — 200 1199 0.74 0.97 239 21.2 341 93

The pulverization time duration was approximately 5 minutes, with d002ranging between 3.3560 and 3.3600, for each case.

With the first method, graphite powders having the density of theinterstitial planar sections of the closure structure followinggraphization as high as 100 or more per μm and the crystallite diameterranging between 100 and 2000 Å were obtained by pulverization employingboth a hammer mill and a disc crusher. It is seen that the density ofthe interstitial planar sections and the crystallite diameter are mainlycontrolled by the rpm of the hammer mill and that of the disc crusher,respectively. If the rpm of the disc crusher is increased, graphitepowders having the density of the interstitial planar sections close toan upper limit of 1500 per μm could be obtained even with the use of thefirst method.

With the second method, graphite powders having an extremely highdensity of the interstitial planar sections of the closed structure andsuperior discharging characteristics comparable to those of Examples 2and 4 could be obtained simply by pulverization using a disc crusher atan rpm of 50 to 200.

Example 7

By the first method, graphite powders were produced in the same way asin Example 1. The graphizing heat treatment was effected for aheat-treatment time duration of 30 minutes, as the rpm of a crusher atthe time of pulverization of the starting material was set to 7500, withthe pulverization time duration of five minutes, 1 wt % of B₄C was addedto the carbon material prior to graphizing heat treatment and as theheat treatment temperature was varied. The density of the interstitialplanar sections of the closure structure and various characteristicvalues of the produced graphite powders are shown in FIG. 4 along withthe discharging capacity and the charging/discharging efficiency.

Example 8

By the second method, graphite powders were produced in the same way asin Example 1. The graphizing heat treatment was effected for aheat-treatment time duration of 30 minutes, as the rpm of a crusher atthe time of pulverization of the starting material was set to 4500, withthe pulverization time duration of five minutes, 1 wt % of B₄C was addedto the carbon material prior to graphizing heat treatment and as theheat treatment temperature was varied. The graphite powders, obtained bygraphizing heat treatment, were subjected to oxidating heat treatment inan oxygen atmosphere at 650° C. for two hours and then to heat treatmentin an argon atmosphere at 1000° C. for five hours. The density of theinterstitial planar sections of the closure structure and variouscharacteristic values of the produced graphite powders are shown in FIG.4 along with the discharging capacity and the charging/dischargingefficiency.

TABLE 4 density of charging/ graphization interstitial B specific meandischarging discharging rpm of temperature planar content surface areaparticle size capacity efficiency method crusher (° C.) sections/μm (wt%) (m²/g) d002 (Å) (μm) (mAh/g) (%) Ex. 7 1 7500 1450 103 0.92 0.613.3693 22.6 291 93 7500 1500 103 0.91 0.62 3.3648 21.8 326 94 7500 2000104 0.89 0.59 3.3601 21.9 334 92 7500 2500 103 0.77 0.64 3.3591 20.8 34291 7500 2900 102 0.61 0.66 3.3568 22 347 92 7500 3000 104 0.53 0.623.3557 19.5 353 94 Ex. 8 2 4500 1450 500 0.94 0.76 3.3694 19.6 297 934500 1500 499 0.92 0.77 3.3647 18.9 330 91 4500 2000 501 0.86 0.73 3.3621.3 339 93 4500 2500 499 0.74 0.75 3.359 20.4 350 94 4500 2900 500 0.640.76 3.3567 22.3 357 95 4500 3000 501 0.52 0.72 3.3556 21.3 362 94

The pulverization time duration was five minutes. The crystallitediameter was 210 to 237 Å, with the mean particle size beingapproximately 21 to 23 μm in each case.

As may be seen from Table 4, the higher the graphization temperature,the smaller is the value of d002, and hence the higher is thecrystallinity. With the crystallinity being higher, thecharging/discharging efficiency was improved without affecting thecharging/discharging efficiency.

Particularly noteworthy is the fact that, by the boron addition, theremay be obtained graphite powders having high crystallinity of not higherthan 3.3650 Å in terms of d002, as a result of which graphite powdershaving a high discharging capacity not lower than 320 mAh/g areobtained. However, if the heat treatment temperature is lower than 1500°C., only graphite powders with d002 higher than 3.3650 Å are obtained,with the discharging capacity being lower.

If no boron is added to graphite powders, it is not possible to producegraphite powders exhibiting high discharging capacity of not less than320 mAh/g, with d002 being not larger than 3.3650 Å, unless thegraphizing heat treatment temperature is set to not lower than 2800° C.It is therefore possible to lower the graphizing heat treatment.temperature by 1000° C. or more by boron addition, thus significantlylowering the manufacturing cost of the graphite powders.

Example 9

By the first method, graphite powders were prepared in the same way asin Example 1. The rpm of the crusher at the time of pulverization of thestarting material was set to 7500, with the pulverization time durationof 5 minutes. To the carbonaceous material, 1 wt % of B₄C was added tothe carbon material prior to graphizing heat treatment and thegraphizing heat treatment was carried out at 2500° C.

The produced graphite powders were classified by sieving for sorting thepowders to a number of groups with different mean particle sizes. Thedensity of the interstitial planar sections of the closure structure andcharacteristic values of the respective groups of the graphite powdersare shown in Table 5 along with discharging capacity andcharging/discharging efficiency.

Also, the bulk density and stability of the electrode plate quality werechecked in the following manner. The results are also collectively shownin FIG. 5.

Bulk Density

The bulk stability of powers is an index of relative ease in charging(chargeability) of the powders and governs the energy density per unitvolume of the electrode. Thus, the bulk density was measured inaccordance with the tap density measurement method prescribed in JISZ2500, with the number of tape being 10. The powder chargeability wasevaluated as being good (∘) and poor (×) if the bulk density is not lessthan 1.17 g/cc and less than 1.17 g/cc, respectively.

Stability of the Electrode Plate Quality

If large-sized particles exist on the electrode plate, the thinseparator plate tends to be pierced to cause shorting. Thus, thegraphite powders in which particles having the particle size exceeding200 μm as measured by the laser diffraction type grain size distributionmeter account for 50 vol % or more were evaluated as being poor (×),with other particles being evaluated as good (∘). These large-sizedparticles are highly likely to be particles of indefinite shape havinglong-axis diameters greatly different from short-axis diameters and aredifficult to remove if the short-axis diameters are smaller than themesh size of the sieve.

Example 10

By the second method, graphite powders were prepared in the same way asin Example 2. The produced graphite powders were classified by sievingfor sorting the powders to a number of groups with different meanparticle sizes. The density of the interstitial planar sections of theclosure structure and characteristic values of the respective groups ofthe graphite powders are shown in Table 5 along with dischargingcapacity and charging/discharging efficiency.

TABLE 5 density of charging/ interstitial B specific mean dischargingdischarging stabilityof rpm of planar sections content surface areaparticle size capacity efficiency bulk electrode method crusher (μm) (wt%) (m²/g) (μm) (mAh/g) (%) density plate quality Ex. 9 1 7500 103 0.721.68 4.3 343 90 x ∘ 7500 103 0.73 0.68 5.4 342 91 ∘ ∘ 7500 104 0.74 0.5432.1 341 95 ∘ ∘ 7500 103 0.71 0.53 37.9 342 96 ∘ x Ex. 10 2 7500 7690.71 1.65 4.4 353 90 x ∘ 7500 770 0.73 0.77 20.3 358 96 ∘ ∘ 7500 7730.71 0.64 34.8 354 95 ∘ ∘ 7500 769 0.77 0.63 38.9 352 95 ∘ x

The pulverization time duration is five minutes. In each case, thecrystallite diameter ranged between 245 and 277 Å, with d002 rangingbetween 3.356 and 3.600 Å.

If the mean particle size of the graphite powders becomes smaller and inparticular to an extremely small size less than 5 μm, thecharging/discharging efficiency of the electrode plate is lowered, whilethe bulk density is lower. On the other hand, if the mean particle sizeof the graphite powders is larger than 35 μm, the electrode platequality is lowered in stability.

Example 11

The present Example is directed to the manufacture of acylindrically-shaped lithium ion secondary battery, configured as shownin FIG. 12, and which makes use of graphite powders obtained in theabove-mentioned Examples 1 to 10 and Comparative Examples 1 and 2.

A negative electrode 1 was fabricated from a negative electrode materialobtained on mixing 90 parts by weight of graphite powders and 10 wt % ofpolyvinylidene fluoride (PVDF) as a binder. This negative electrodematerial was dispersed in N-methyl pyrrolidone to prepare a paste-likeslurry which was then coated on both sides of a strip-shaped copperfoil, 10 μm in thickness, which subsequently serves as a negativeelectrode current collector 9. The resulting assembly was dried andcompression-molded to prepare a strip-shaped negative electrode 1.

A positive electrode 2 was fabricated from LiCoO₂, obtained on firing amixture of 0.5 mol of lithium carbonate and 1 mol of cobalt carbonate inair at 900° C. for five hours. The results of X-ray diffractometryindicated good coincidence of the produced LiCoO₂ with the peak ofLiCoO₂ registered in the JCPDS file. This LiCoO₂ was pulverized andclassified to LiCoO₂ powders having a 50% cumulative particle size of 15μm. 95 parts by weight of the LiCoO₂ powders and 5 parts by weight oflithium carbonate powders were mixed together to form a powder mixture.95 parts by weight of the resulting powder mixture, 6 parts by weight ofthe electrically conductive graphite and 3 parts by weight of PVDF as abinder were mixed to prepare a positive electrode material. Thispositive electrode material was dispersed in N-methyl pyrrolidone tofrom a paste-like slurry which was uniformly coated on both sides of astrip-like aluninum foil, 20 μm in thickness, which later serves as apositive electrode current collector 10. The resulting assembly wasdried and compression-molded to form a strip-like positive electrode 2.

The strip-like negative electrode 1, strip-like positive electrode 2 andseparators 3, formed by micro-porous polypropylene films 25 μm inthickness, were layered in the order of the strip-like negativeelectrode 1, separator 3, strip-like positive electrode 2 and theseparator 3, and the resulting layered product was wound about itself anumber of times to form a spirally-shaped electrode member having anoutside diameter of 18 mm. This spirally-shaped electrode member washoused in a nickel-plated iron battery can 5. An insulating plate 4 wasarranged on the top and the bottom of the spirally-shaped electrodemember. An aluminum positive terminal lead 12 was led out from thepositive electrode current collector 10 and welded to a battery cap 7,whilst a nickel negative terminal lead 12 was led from the negativeterminal current collector 9 and welded to the battery can 5.

Into the battery can 5, housing this spirally shaped electrode member, a1M solution of LiPF₆ dissolved in a mixed solvent of ethylene carbonateand diethylene carbonate bearing a 1:1 volume ratio of ethylenecarbonate to diethylene carbonate was charged as an electrolyte. Asafety valve device 8 having a current breaking mechanism and a batterylid 7 were caulked to the battery can 5, via a insulated sealing gasket6 having an asphalt surface coating, to prepare a secondary batteryhaving a non-aqueous electrolytic solution, with a diameter and a heightof 18 mm and 65 mm, respectively.

50 batteries were tentatively manufactured, for respective groups ofgraphite powders, and the following evaluation was made of theperformance of these batteries. The results of the evaluation are shownin Table 6 along with the performance of the negative electrodes of thegraphite powders used for the negative electrodes (discharging capacityand charging/discharging efficiency of the negative electrodes).

Method for Evaluation of Batteries

-   1) Charging Conditions: The batteries were charged for 2.5 hours    under the maximum charging voltage of 4.2 V and the current    intensity of 1 A.-   2) Discharging Conditions: The batteries were discharged up to 2.75    V with the constant current of 700 mA.-   3) Battery Capacity: The discharging capacity was found by measuring    the discharging time until the battery capacity reached 2.75 V with    the constant current of 700 mA. If this time is 2.2 hours, 700    mA×2,2 h=1540 mAh is the discharging capacity. The    charging/discharging was replaced under the above-mentioned    conditions and the maximum discharging capacity obtained for the    initial two to five cycles was used as the battery capacity. In the    present Example, the battery capacity is a mean value of the battery    capacities of 50 batteries.

TABLE 6 discharging battery capacity Ex. Nos. capacity (mAh/g)efficiency (%) (mAh) Ex. 1 341 92 1584 342 93 1594 344 93 1599 328 941569 340 92 1582 Ex. 2 357 92 1622 Ex. 3 343 96 1620 342 96 1617 343 911581 341 85 1530 342 81 1501 Ex. 4 356 86 1650 357 90 1606 Ex. 5 348 931608 340 94 1597 344 92 1591 358 91 1616 359 92 1626 361 94 1647 Ex. 6349 93 1611 344 91 1583 341 93 1592 Ex. 7 291 93 1474 326 94 1564 334 921568 342 91 1579 347 92 1598 353 94 1628 Ex. 8 297 93 1488 330 91 1551339 93 1587 350 94 1621 357 95 1645 362 94 1649 Ex. 9 343 90 1573 342 911579 341 95 1607 342 96 1617 Ex. 10 353 90 1597 358 96 1655 354 95 1638352 95 1633 Comp. Ex. 1 305 94 1515 321 93 1545 325 93 1554 Comp. Ex. 2317 94 1542 315 89 1512 316 82 1438

It is seen from Table 6 that, with the use of a negative electrodematerial according to the present invention, a lithium ion secondarybattery superior in both the capacity and the efficiency can beproduced.

1. A graphite powder formed by graphitization at a temperature rangingfrom about 1500° C. to less than 2200° C., the graphite powdercomprising a carbon material containing less than 1.0 wt % of boron andhaving a looped closure structure at an end of a graphite c-planar layeron at least a surface of cleavage formed by shearing, wherein thedensity of the interstitial planar sections between neighboring closurestructures is not less than 100/μm and not more than 1500/μm.
 2. Anegative electrode material of a lithium ion secondary battery, thenegative electrode material consisting essentially of a graphite powderformed by graphitization at a temperature ranging from about 1500° C. toless than 2200° C., the graphite powder comprising a carbon materialcontaining less than 1.0 wt % of boron and having a looped closurestructure at an end of a graphite c-planar layer on at least a surfaceof cleavage formed by shearing, wherein the density of the interstitialplanar sections between neighboring closure structures is not less than100/μm and not more than 1500/μm.
 3. A lithium ion secondary batterycomprising: a negative electrode material consisting essentially of agraphite powder formed by graphitization at a temperature ranging fromabout 1500° C. to less than 2200° C., the graphite powder comprising acarbon material containing less than 1.0 wt % of boron and having alooped closure structure at an end of a graphite c-planar layer on atleast a surface of cleavage formed by shearing; a positive electrodematerial comprising LiM¹ _(1-x)M² _(x)O₂ or LiM¹ ₂yM² _(y)O₄, where xand y are numerical figures such that 0<x<4 and 0<y<1 M¹ and M² denoteat least one of the transition metal of Co, Ni, Mn, Cr, Ti, V, Fe, Zn,Al, In and Sn and, a nonaqueous electrolyte, wherein said negativeelectrode material and positive electrode material are coated on bothsides of respective current collector, wherein the density of theinterstitial planar sections between neighboring closure structures isnot less than 100/μm and not more than 1500/μm.
 4. A graphite powderformed by graphitization at a temperature ranging from about 1500° C. toless than 2200° C., the graphite powder comprising a carbon materialcontaining less than 1.0 wt % of boron and having a looped closurestructure at an end of a graphite c-planar layer on at least a surfaceof cleavage formed by shearing, wherein the graphite powder furthercomprises a c-axis (002) planar section lattice distance (d002) that is3.3650 Å or less as determined by a lattice constant measurement methodby x-ray diffraction.
 5. A negative electrode material of a lithium ionsecondary battery, the negative electrode material consistingessentially of a graphite powder formed by graphitization at atemperature ranging from about 1500° C. to less than 2200° C., thegraphite powder comprising a carbon material containing less than 1.0 wt% of boron and having a looped closure structure at an end of a graphitec-planar layer on at least a surface of cleavage formed by shearing,wherein the graphite powder further comprises a c-axis (002) planarsection lattice distance (d002) that is 3.3650 Å or less as determinedby a lattice constant measurement method by x-ray diffraction.
 6. Alithium ion secondary battery comprising: a negative electrode materialconsisting essentially of a graphite powder formed by graphitization ata temperature ranging from about 1500° C. to less than 2200° C., thegraphite powder comprising a carbon material containing less than 1.0 wt% of boron and having a looped closure structure at an end of a graphitec-planar layer on at least a surface of cleavage formed by shearing; apositive electrode material comprising LiM¹ _(1-x)M² _(x)O₂ or LiM¹ ₂yM²_(y)O₄, where x and y are numerical figures such that 0<x<4 and 0<y<1 M¹and M² denote at least one of the transition metal of Co, Ni, Mn, Cr,Ti, V, Fe, Zn, Al, In and Sn and, a nonaqueous electrolyte, wherein saidnegative electrode material and positive electrode material are coatedon both sides of respective current collector, wherein the graphitepowder further comprises a c-axis (002) planar section lattice distance(d002) that is 3.3650 Å or less as determined by a lattice constantmeasurement method by x-ray diffraction.